Azo dye



Patented Aug. 5, 1941 AZO DYE Byron L. West, Plainfield, and Dale R. Eberhart,

Middlesex, N. J., assignors, by mesne assignments, to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application May 23, 1939, Serial No. 275,152

Claims.

This invention relates to azo dyes, and. moreparticularly to acid wool azo dyestuifs and their preparations.

According to the present invention, we have found that azo dyes having the following general formula:

in which R is a nitro, amino, acylamino or aryl azo radical, R. is the radical of an aromatic coupling component, and

While the invention in its broader aspect cov- I ers dyes in which R is the radical of any aromatic coupling component, we prefer those in which R contains a solubilizing group such as a sulfonic acid group- These preferred acid azo dyestuffs are particularly useful in the dyeing of wool, but it should be understood that the present invention is not limited to the preferred embodiments.

The dyestuffs of the present invention may be prepared by diazotizing a 4-nitroaniline-2-sulfonamide described in our copending application, Serial No. 275,153, filed May 23, 1939, coupling the resulting diazo compound with a suitable coupling component, and reducing the nitro group. If desired, the amino group so obtained may then be acylated or it may be diazotized and coupled with an aromatic coupling component.

If a monoazo dye is desired, it is possible to start with a 4-acylaminoaniline-2-sulfonamide, diazotize it, and then couple on a suitable coupling component.

Sulfonamides having the following general formula:

CH2--OH2 SOzN \Y CH2CH2/ in which Y is O or S and which are derivatives of morpholine or thiomorpholine respectively, are the preferred starting materials of the present invention. However, it should be understood that the invention is in no sense limited to these preferred embodiments and in its broader aspects also includes sulfonamide derivatives of monoalkylpiperazines.

Various coupling components are suitable for use in the present invention. Examples of coupling components useful for the preparation 0! acid wool dyestufis are the Cleve acids, aminonaphthol sulfonic acids such as 2-amino8- naphthol-G-sulfonic acid (Gamma acid), 2- amino-5-hydroxynaphthalene-7-sulfonic acid (J acid), 1-hydroxy-8-aminonaphthalene-3,6-disulionic acid (H acid). Other typical coupling components are ice color coupling components such as arylides of 2-hydroxy-3-naphthoic acid or acetoacetic acid, pyrazolones, aminoazo compounds, mononuclear amines, and the like.

The monoazo and disazo dyes prepared according to a preferred embodiment of the present invention where R is acylamino and R is a sulfomc acid of the naphthalene series dye animal fibers, and particularly wool, in red to violet shades. They dye levelly and possess excellent fastness to light; hence, they are particularly useful in the dyeing of carpet materials.

The invention will be described in greater detail in conjunction with the following specific examples which are only illustrations and not intended to limit the invention to the specific details therein set forth. The parts are by weight.

EXAMPLE 1 Preparation of intermediate 256 parts of i-nitrochlorobenzene-Z-sulfon chloride are added to 450 parts of water at room temperature, followed by the addition of 90 parts of morpholine. A 20% sodium hydroxide solution is added with agitation until the pH of the mixture is between 9 and 11. After stirring. for 10 minutes, the mixture is heated to 90 C. during about 1 hour. The pH of the reaction is kept between 9 and 11 by the addition of sodium hydroxide solution. Between the temperatures of 72 and 75 C. heating is stopped and a little ice added to keep the temperature from rising too rapidly if the reaction becomes too vigorous.

About 40 parts of sodium hydroxide solution are heated to 55 C. for 5 minutes, made slightly required. When the reaction is complete, the acid (pH about 6) with acetic acid, iced to 25 C., batch is cooled to 70 C., filtered, and washed and 128 parts of acetic anhydride added quickly. until free from alkali. After stirring for 30 minutes, the dye is heated The 4-nitrochlorobenzene-2-sulfonmorpholide o to 60 C., salted out with 1050 parts of salt is charged into a suitable autoclave along with and filtered. The product is dried in air at 60 C. 900 parts of water and 255 parts of 29.9% amto give about 400 parts of a dark red powder monium hydroxide. The batch is then heated to which dyes wool bright red shades of excellent 100 C. in about'l hour, then to 130 C. in an adfastness to light. ditional 30 minutes, and held at 130 C. for 10 1;: The formula of the dyestufi obtained is:

hours. The maximum pressure developed is about 60 pounds. After cooling to 60-75 C., the OH autoclave is discharged and the batch is filtered, HZN

washed until free from alkali, and dried in air at 'zo so c. 1:, SOzN $03K Diazotization 287 parts of the 4-nitroaniline-2-sulfonmor pholide are thoroughly mixed with 13 partsof EXAMPLE 2 glacial acetic acid and then sprinkled into nitro- 237 parts of 4 nitmani1ine 2-suHOnmorDholide syl sulfuric acid from 1870 parts of 93% sulfuric is diazotized as i Example 1, coupled to 272 i and Parts of Sodium nitrite during 30 A parts of H acid (monosodium salt) which has mmutes holding i temperature between been acidified with 116 parts of 36% hydrochloric d i 'i 1S 2 15 about 2 acid. After stirring for 16 hours, the dye is minu es a 15 empera ure an en rowne in 5600 parts of ,water and 3350 parts of ice. This 23 zi zfifi g g i ifi $33 223:ig ggfi i gg 'gz g gi izg minutes; and the dlazo dye is slightly alkaline, then 104 parts of sodium 1 I eou Zing carbonate is added, the mixture is iced to 0 C., p and the diazo compound from 74.4 parts aniline,

, To approximately two-thirds of the filtered 39 55.2 parts of sodium nitrite and 66 parts of diazo compound is added over a period of 5-10 hydrochloric acid is added. After coupling is minutes a solution of Gamma acid (2-aminocomplete, the dye is isolated in the usual way S-napthol-G-sulfonic acid) made up from 196 by salting and dyes animal fibers a green shade parts of Gamma acid in 2000 parts of water, 32 of blue. parts ofysodium hydroxide and sufficient acetic 3-3 The formula of the dyestufi is as follows:

SOzN O acid to make the solution permanently acid to EXAMPLE 3 v litmus. The remainder of the diazo compound The dye of Example 2 is further treated by addefi 2 fast as filtered- The dye 1S filtered reduction with sodium sulfhydrate, followed by after stirring for about 2 hours. acetylation in the usual manner to give a prod- V Reduction uct that dyes anima1 fibers green shades of blue, 1 redder than the product of the preceding ex- The nitro dye from the 287 parts of 4-nitroample. aniline-2-sulfonmorpholide is suspended in wa- The formula of the dyestufi obtained is:

. 0 0 H ONHC N=N N=NC K HSo son SOgN 0 a C2114 V I ter, heated to c., and brought to a pI-I of V EXAMPLE 4 7.5 to8.5 by the addition of approximately 172 parts of sodium hydroxide. Then a solution containing 128 parts of sodium sulfhydrate is added. The temperature rises to about 50 C. and after P s O J acid in acid d um at 5-10 C. The stirring for 30 minutes, the dye is salted out and precipitated dye S fi te ed W t s S- i pended in 16,000 parts of water, neutralized 287 parts of 4-nitroaniline-2 sulfonmorpholide is diazotized as in Example 1 and coupled to 192 filtered.

l A l 7 with sodium hydroxide, 104 parts of sodium car- 5 66 bonate added, and iced to 0 C. Diazobenzene The reduced dye from 287 parts of 4-nitroprepared in the usual manner from 74.4 parts aniline-2-sulfonmorpholideis added to suflicient aniline, 55.2 parts sodium nitrite and 66 parts water to just dissolve it at 50 C., then it is hydrochloric acid is added until the diazo test persists at least 30 minutes. The dye is filtered EXAMPLE 8 without salting to give a product dyeing animal fibers brown-red shades. If the 1-phenyl-3-methyl-5-pyrazolone of the The formula of the dyestufi obtained is: i preceding example is substituted by 1-(2-chloro- EXAMPLE 6 -sulfophenyl) -3-methyl-5-pyrazolone, a bright ter-soluble dye is produced which can The dye of Example 4 is further treated by reyellow duction with sulfhydrate, followed by acetylation further treated t h Sulfide j to in known manner. Salting and filtration give a new the correspondvmg ammo dye Whlch m tum product that dyes animal fibers red shades much by acetylation produces a dye of greener yellow yellower and brighter than the dye of Example 4. shades f d br h n ss n win n s nsi- The formula of the dyestuil obtained is: tivity to alkali.

0 H3O ONH N=N-- /C2H4\ H2N SO3H SO2N\ /o O C2H4 EXAMPLE 6 The formula of the dyestuff obtained is:

A diazo solution prepared from 287 parts of 4- nitroaniline-2-sulfonmorpholide as in Example 1 CmCONEF fi is added to an iced alkaline solution of 270 parts /C2H4 of the anilide of 2-hydr0xy-3-naphthoic acid in SOZN O N 16,000 parts water along with sufficient sodium hydroxide as solution to neutralize the acid of the 2 diazo solution. The color separates as a bright 01 red precipitate which may be filtered off, dried and ground to a bright red powder. The same SO H dyestuiii may be produced also on the fiber 3 padded with the anilide of 2-hy'droxy-3-naph- EXAMPLE 9 thoic acid- I 40 The diazo solution prepared from 287 parts of The formula of the dyestuff Obtamed 1S3 4-nitroaniline-2-sulfonmorpholide as in Example 1 is added to a solution of 107 parts of m-toluidine in 4000 parts water and 3'7 parts H01 (100%) iced to 0 C. After stirring 20 minutes, the acidity is O2NON=N reduced by the addition 012 000 parts of sodiumozm I acetate crystals. Coupling is then finished in I on 0on0 20-40 minutes. After stirring two hours longer,

S ON 0 the product is filtered and dried to yield 440 parts 0211., of a brick red powder, which is soluble in acetone as a red-orange solution, and dyes cellulose ace- EXAMPLE 7 tate fibers a salmon shade when dyed in the usual The diazo solution prepared from 287 parts of manner. The product is a useful intermediate for 4nitroaniline2-su1f0nmorph0lide as in Example direct dy Of a e y Of Shades- Reduction of 1 is added slowly to an iced slightly alkaline soluthe nitrO group of this P uct it er be ore or tion of 176 parts of 1-phenyl-3-methyl-5-pyrazo after diazotization produces other valuable prodlone in 6000 parts of water. Sufiicient sodium hyucts.

droxide solution is added to permit completion The formula of the dyestuff obtained is: of coupling in 10 to 15 minutes. About 4800 parts of a 20% sodium hydroxide solution are required. The coupling mixture at completion is still acid to Congo Red paper. The dye separates at once 02N*C N=N NH2 as a bright yellow precipitate which may be filtered ofi, dried and ground to yield a bright O 0 orange yellow powder insoluble in water.

The formula of the dyestuff obtained is:

EXAMPLE 10 O2N fi fi In the preceding example, the 107 parts of ml /C2Hi HOO\ N toluidine are substituted by 137 parts of cresidine. SOzN o N Coupling is complete in this case without addition of sodium acetate or other neutralizing agent. Filtration and drying yield a dark red powder which is soluble in acetone as blue-red solution and dyes cellulose acetate fibers blue shades of pink when dyed in the usual manner.

nitro group of this product either before or after diazotization produces other valuable products.

The formula of the dyestuff obtained is:

(SCH: SOzN 021314 EXAMPLE 11 a The amino dye of Example 1 (571 parts of 100%) is dissolved in about 14,000 parts of water at a temperature suitable for complete solution (slightly alkaline), 69 parts of 100% sodium nitrite is added, and when solution is complete, the dye solution is run into a mixture of 144 parts of 100% H01 and sufficient ice so that the final temperature is -5 C. After stirring 15 minutes, the diazo solution is run into a solution of 230 parts of 1-naphthol-4-sulfonic acid and 318 parts of NazCOs in 2000 parts of water iced to 0 C. After stirring 2 how's, the product is salted, filtered and. dried to give a dark powder which dyes vegetable fibers a bright green blue shade and animal fibers redder shades of blue.

The formula of the dyestufi obtained is:

SOaH

S0311 O2H4/ What we claim is: c 1. An azo dyestufif having the following general formula: c i

in which R is a member of the group consisting of nitro, amino, and acylamino radicals and R is an aromatic coupling component; i

2. An azo dyestufi having the following general formula:

CHzCONH in which R is a radical of the naphthalene series containing a sulfonic acid group.

3. An azo dyestuif having the following for mula:

SOzN 0 4. An azo dyestuff having the following formula:

SOaN O 5. An azo dyestufi having the mula:

following for- 

